Mineral oil composition



preferred.

Patented Nov. 4, 1 952 UNITED STATS MINERAL OIL COMPOSITION John J. Giammaria, Woodbury, N. J., assignor to Socony-Vacuum Oil Company, Incorporated, a corporation of New York No Drawing.

Application June 21, 1947,

Serial No. 756,316

8 Claims.

This invention relates to improved lubricating oil compositions and, more particularly, to lubricating oil compositions improved by the addition of small percentages, suflicient to improve the characteristicsof the oil, of products formed by copolymerizing alpha, beta-unsaturated polycarboxylic acids or acid anhydrides with esters of allyl alcohol, and thereafter esterifying the products with normal aliphatic alcohols, or mixtures of normal aliphatic alcohols, containing between about eight and about eighteen carbon atoms per molecule.

, Prior to this invention alpha, beta-dicarboxylic acids, their anhydrides, and their esters have been mentioned in the literature as being copolymerizable with unsaturated compounds. However, insolar as is known, it has never before been suggested that alpha, beta-polycarboxylic acids or their anhydrides could be copolymerized with allyl estersand that the copolymers so formed could thereafter be esterified with relatively long chained, normal aliphatic alcohols to yield oilsoluble products which could be added to lubricating oils to lower the pour points or improve the viscosity indexes thereof.

According to the present invention, it has been found that alpha, beta-polycarboxylic acids or their anhydrides will react with allyl esters to produce copolymers, which copolymers are still capable of reacting with normal aliphatic alcohols to form new compositions of matter. It has further been discovered that at least certain of the compositions of matter so formed can be added to lubricating oils in minor proportions and that the addition will lower the pour points and improve the viscosity indexes of the lubricating oils.

REACTANTS The reaction products of this invention are prepared from three basic reactants, a po1ycarboxylic acid material, an allyl ester material, and a normal aliphatic alcohol material. To these three basic reactants a fourth material, which may be designated as a vinyl monomer, may be added. 1 l

The polycarboxylic acid'material may consist of a singlechemically pure alpha, beta-unsaturated polycarboxylic acid such as maleic acid, fumaric acid,itaconic acid, glutaconic acid, mesaconic acid; citraconic acid, or aconitic acid. It may, instead, consist of a single, pure anhydride of such an acid or a mixtureof such acids or anhydrides, or a single commercial quality acid or anhydride or a mixture of such acids or anhydrides. In general, the use of the anhydrides is Substituted acids such a chloromaleic acid may also be used. Maleic and fumaric acids, and particularly maleic anhydride, are preferred because of their availability, and the ease with which they react.

The allyl ester material may similarly be either of chemically pure quality or of commercial quality and may consist of either a single allyl ester or a mixture of allyl esters. These may be derived either from monoor polybasic acids including aliphatic straight or branched chain acids, 'or from aromatic acids. Examples are allyl acetate, allyl-2-ethylhexoate, allyl stearate, diallyl sebacate, allyl benzoate and diallyl phthalate. Preferably this material contains between about eight and about eighteen carbon atoms per molecule and, better still, an average of about fourteen atoms per molecule, that is to say, an average of not less than twelve nor more than sixteen.

The normal, aliphatic alcohol material used for the final esterification may be either a single, chemically pure, normal, aliphatic alcohol, a commercial grade of normal, aliphatic alcohol, or a mixture of chemically pure or commercial grade normal, aliphatic alcohols. The average number of carbon atoms per molecule of alcohol should preferably be not less than about eight nor more than about eighteen, and better still about fourteen, that is to say, not less than twelve nor more than sixteen. A technical grade of lauryl alcohol as sold by Eastman Kodak Company may be named as a preferred example. Commercial alcohol mixtures such as Lorol-B and Lorol- 5, manufactured byE. I. du Pont de Nemours 8: Company, have also been found very satisfactory. These alcohol mixtures contain alcohols ranging from ten to eighteen carbon atoms per molecule in approximately the following proportions:

Lorol-B Lorol-5 Percent Percent Av. No. 0 Atoms 13. 5 l2 7 REACTION CONDITIONS The copolymerization of the allyl ester material and the polybasic acid material, may beaccomplished by heating at temperatures ranging from about 50 C. to about C. for a period of time sufiicient to accomplish the desired re action. Periods of from one to twenty-four hours have been found satisfactory. The reaction can be accomplished either in the presence or the absence of solvent. Among the preferred polymerization catalysts is benzoyl peroxide in a proportion of about 0.10 to about 5.0% by weight. Solvents, such as benzene, xylene, or dioxane, may be added toreduce the viscosity and to -control the reaction more efiiciently.

In the case of a peroxide catalyzed polymerization, according to the literature (P. D. Bartlett and Kenzie Nozaki, The Polymerization of Allyl Compounds-The Peroxide Induced ,Copolymerization of Allyl Acetate with; Maleicnnhydridefi? J. A. C. S., August 1946, page;l ;4;9 5 );a;lglpolymer composition always results.

Although the ratio of reactantsin the copolymer may remain constant, the reaction conditions will affect the length of the copolymer chain. For example, the use of low temperatures, small amounts of peroxide catalysts and long reaction wi re u h g e mo e ular Weight co- .pgl-yrners. By conducting the reaction in the .absenqe ee ent Q i eresenc o s vents. such as dioxane, which-do not tend to cause chain transfer, there is an increased tendency toward theformation of higher molecular weight poly- .mers.

The esterification of the copolymer .with the alcohol material -may be accomplished by simply heating the copolymer and the ,alcohol -material in thepresenceof a small amount of concentrated sulphuric ,acidor-p-toluene sulphonic acid. Itis .prefer-redin thisreactionto utilizeahig-h-boiling solvent such as xylene :and -azeotropica1ly distill the water formed in the-reaction.

in another embodiment of the present inven ;tio =a v r .y m n me fiuch a in l a a ty- :-e .e v ri u i y -;e o :eth s. is c polyerizss w thanal y es er-andmale anhy or e am l d t copol me thu obta ed isthen esterifled with ithe alcohol material. A

fairlywide range of proDQrtiOns of vinyl monomer ito-copolymer may beused for example, from none atall up to at least 50% by weight of theweight of-thecopolymer. Preferably-if a vinyl monomer isto beused at all, it will housed in the proportion of about i .to-,-30% based-,on-the weight of th c o yme OIL BASE The reaction products of this invention are particularly adapted for use as pour point depressants and viscosity index improvers in lubricating oils. They may be incorporated in 'any type of 'lubricating'oil rangingfrom-gasolineand'keromm to petrolatum and petroleum-wax. They may also be used in synthetic lubricating oils or even inlubricating oils or otherlubricants derived from animal or vegetable sources. The reaction products of this invention are particularly adapted for use in petroleum oils of the type normally used for: the lubrication of internal combustion engines.

, CONCENTRATION IN .O'ILS The reaction products of this invention will normally be incorporated in lubricating oils in '4 ucts in the oil, a concentration of 0.01% to 2.0% is preferred.

It is within the concept of this invention to incorporate the new reaction products in oils containing other improving agents such as pour depressants, detergents, extreme pressure lubrication improvers, viscosity index -,improvers, stabilizing agents, rust inhibitorsand the like.

It is further contemplated that the reaction :products of this invention may be prepared and marketed in their pure form, that is, without admixture with lubricating oils, or may be prepared andmarlsetedin concentrated solutions in oil, --whic h-lconcentrated solutions are adapted to be added to further-quantities of oil to improve its characteristics.

Further details of this invention and further advantages may be understood from the following detailed examples and results of tests.

Emample I A copolymer, of .allyl laurate and maleic anhydride was prepared by first preparingallyl laurate from allyl alcohol and a technical grade of lauric acid-and reacting 50.0 g. of thisallyl laurate with 20.2 g. of maleic anhydride in the-presence of 0.7 .g. of benzoyl peroxide and200 cc.'of xylene. The reactants were mixed and slowly heated to xylene reflux temperatureand held at that temperature for four hours. The xylene and unreacted materials .wereremoved by distillation at C. under 0.5 mm. mercury pressure. The copolymer was anamber-colored resin.

20.0 g. of the copoIymerand GOD-g. of Lorol- B were reacted in the presenceof 0.8 g. of p-toluene sulphonic acid and 100 cc. of xylene by heating to xylenereflux temperature in a flask equipped with aside arm water trap and condenser. ;After; heating; for 1 hour the xy1e,ne was slowly removed by distillation, raisin the temperatureto C. and heatingfor ariadditional hour. The solution was transferred toadistillingflask and the remainingxyleneand unreacted alcohol removed bydi-stillation at 250 r C. under 1 mm. m-ercmyofpressure. The viscous polymer which resultedwas readily soluble in lubricating oil.

Instead of distilling at high temperatures to remove unreacted high molecular weight alcohols, extraction with hot alcohol may be used. For examplethe copolymer after removal of solvent, maybe extracted severaltimes with about3 to-5 volumes of, hot alcohol, preferably ethyl alcohol. The high molecular'weight alcohols are soluble in the vh-o-t,alcohol While :the copolymers are insoluble therein. Traces ,of entrained alcohol are removed by evaporation on a steam bath.

Jammnlel A copolymer of "allyl; acetate and :maleic anhydridewas meparedibyzreactingvfimo g. of allyl acetate and 19.01g. of smaleic anhydride in the presenceof {3.0 g. of benzoyl peroxide in 400 cc. of toluene. The reactants were mixed and heated to reflux temperature as before. Afterabout 15 minutes, the -copolymer began to precipitate from the-solution. Themixturewasheated fori3 hours, coolediand filtered. The copolymer was dissolved, in dioxane and :repreclpitated "by pourmg into water. It-was'then vacuum filtered and dried to-a white resin.

, 10.0 g. of this'copolymer and-22.0 g. of "Lorol- B "were reacted in'the presence of 0.3 g. ofconcentrated sulphuricacid and 250 cc. of xylene. i fhercaction was accomplishedassin. Example'l.

except that a reaction time of 6 hours was used. The viscous product was readily soluble in lubricating oil.

Example III A copolymer of allyl oleate and maleic anhydride was prepared by reacting 50.0 g. of allyl oleate and 25.0 g. of maleic anhydride in the presence of 1.0 g. of benzoyl peroxide in 200 cc. of dioxane. The solution was heated at 80 C. with stirring for 24 hours. It was then poured into water to precipitate the copolymer which was vacuum filtered and dried.

16.0 g. of this copolymer and 36.0 g. of Lorol- B were reacted in the pressure of 1.0 g. of concentrated sulphuric acid and 150 cc. of xylene. The reaction was conducted as in Example I. The finished ester was readily soluble in lubrieating oil.

Example IV 1 A copolymer of diallyl sebacate and maleic anhydride was prepared by reacting 60.0 g. of diallyl sebacate with 40.0 g. of maleic anhydride inthepresence of 1.0 g. of benzoyl peroxide and 200 cc. of dioxane. The reaction was accomplished in the same manner as in Example III.

20.0 g. of this copoly-mer were reacted with 40.0 g. of Lorol-B in the presence of 1.0 g. of concentrated sulphuric acid and 150 cc. of xylene, as in Example I. The ester was readily soluble in lubricating oil.

Example V A copolymer of allyl benzoate and maleic anhydride was prepared by reacting 65.0 g. of allyl benzoate with 40.0 g. of maleic anhydride in the presence of 1.0 g. of benzoyl peroxide and 200 cc. of dioxane. The reaction was accomplished as in Example III.

15.0 g. of the copolymer were reacted with 35. g. of Lorol-B in the presence of 1.0 g. of concentrated sulphuric acid and 150 cc. of xylene as in Example I. The ester was readily soluble in lubricating oil.

Example VI 16.3 g. of maleic anhydride, 20.0 g. of allyl laurate (prepared from allyl alcohol and Eastmans technical lauric acid), 8.3 g. of freshly distilled vinyl acetate and 0.45 g. of benzoyl peroxide were slowly heated to 95 C. At this point vigorous reaction took place, the temperature rising to 155 0. despite the fact that the reaction flask was cooled by means of an ice bath. The reaction product was a sticky, resinous mass which was diluted with 150 cc. of dioxane and heated at reflux for 1 hour. The dioxane was then removed by distillation.

10.0 g. of the above copolymer were mixed with 18.0 g. of Lorol-B, 0.5 g. of p-toluene sulphonic acid and 200 cc. of xylene and heated at xylene reflux for 3 hours in a flask equipped with a side arm water trap and condenser. The solution was cooled, washed with water and filtered. Solvent and unre'acted alcohol were distilled by heating to 280 C. under 1 mm. pressure.

Example VII A copolymer similar to Example VI was prepared except that the copolymerization was run in the presence of 100 cc. of dioxane at reflux for 8 hours. A Lorol-B ester of this copolymer .was prepared as described above.

The effectiveness of the reaction products prepared in accordance with the above examples, as depressants of the pour point of lubricating oils, is illustrated by the data ofTable I, which follows: These results were obtained by blending 0.25% by weight of the selected reaction product into a furfural-refined Mid-Continent type base oil having an original ASTM pour point of +20 F.

as viscosity index improvers is illustrated by Table II which follows. These results were obtained by blending 1.0% of the selected reaction product with an acid refined, Mid-Continent type base oil having an original viscosity index of 78.5

TABLEII' Kinematic Compounds g Viscosity- Viscosity l Weight Index m 011 Percent at 100 F. at 210 F.

None 30. 55 4. 82 73. 5 Example III 1. 0 31. 29 4. 85.4 Example V l. 0 31.00 4.94 86. 9

What is claimed is:

l. A mineral lubricating oil containing from about 0.01 per cent to about 20 per cent by weight of a reaction product formed by reacting an allyl ester with an alpha, beta-unsaturated material selected from the group consisting of alpha, betaunsaturated dicarboxylic acids and their anhydrides, and esterifying the product of this reaction with a normal aliphatic alcohol containing from about 8 to about 18 carbon atoms.

2. A mineral lubricating oil containing from about 0.01 per cent to about 20 per cent by weight of a reaction product formed by reacting an allyl ester of an aliphatic monobasic acid containing from about 8 to about 18 carbon atoms with an alpha, beta-unsaturated material selected from the group consisting of alpha, beta-unsaturated dicarboxylic acids and their anhydrides, and esterifying the product of this reaction with a normal aliphatic alcohol containing from about 8 to about 18 carbon atoms.

3. A mineral lubricating oil containing from about 0.01 per cent to about 20 per cent by weight of a reaction product formed by reacting an allyl ester of an aliphatic monobasic acid containing from about 8 to about 18 carbon atoms with an alpha, beta-unsaturated material selected from the group consisting of alpha, beta-unsaturated dicarboxylic acids and their anhydrides, and esterifying the product of this reaction with a mixture of normal aliphatic alcohols containing from about 10 to about 18 carbon atoms and having an average of about 14 carbon atoms per molecule.

4. A mineral lubricating oil containing from about 0.01 per cent to about 20 per cent by weight of a reaction product formed by reacting allyl laurate with maleic anhydride and esterifying the product of this reaction with a mixture of normal aliphatic alcohols containing from about 10.:tn; about 18 carbon atoms and. having: an average-of. about-14 carbon atoms; per molecule. A mineral lubricating; oil; containing. from about 0.01 per. cent'to about 20 per cent by weight of a reaction product: formed, by reacting, allyl oleate with maleic anhydride and esterifying the product of this reaction with a mixture of normal aliphatic alcohols containing from about 10 to about 18 carbon atoms and. having an average of about- 14 carbon atoms permolecule.

6. A mineral lubricating oil containing from about 0.01 per cent to about 20 per cent by weight of a reaction product formed by reacting allyl benzoate with maleic anhydride and esterifying the product of this reaction with a mixture of normal aliphatic alcohols containing from about '10 to about 18 carbon atoms and having, an average of about 14 carbon atoms per molecule.

7. A mineral lubricating oil containing from about 0.01 per: cent" to about20' percent by weight of a reaction product formed by reacting allyl seb'acate with maleic anhydride and esterifying theproduct of this reaction with a mixture of normal aliphatic alcohols containing from about IO-toabout 18 carbon atoms and having an average of about 14 carbon atoms per molecule.

8. A mineral lubricating, oil containing; from about 0.01'per centto about 20 per cent by weight of a reaction product formed by reacting allyl acetate with maleic anhydrideand esterifying the product of this reaction with a mixture of normal aliphatic alcohols containing from about 10 to about 18 carbon atoms, and having an average of about 14 carbon atoms per molecule.

JOHN J. GIAMMARIA.

REFERENCES CITED The following references are of record in the file of this patent:v

UNITED. STATES PA'I'ENTS 

1. A MINERAL LUBRICATING OIL CONTAINING FROM ABOUT 0.01 PER CENT TO ABOUT 20 PER CENT BY WEIGHT OF A REACTION PRODUCT FORMED BY REACTING AN ALLYL ESTER WITH AN ALPHA, BETA-UNSATURATED MATERIAL SELECTED FROM THE GROUP CONSISTING OF ALPHA, BETAUNSATURATED DICARBOXYLIC ACIDS AND THEIR ANHYDRIDES, AND ESTERIFYING THE PRODUCT OF THIS REACTION WITH A NORMAL ALIPHATIC ALCOHOL CONTAINING FROM ABOUT 8 TO ABOUT 18 CARBON ATOMS. 